Method for producing 2,3,3,3-tetrafluoropropene

ABSTRACT

This invention provides a method for producing 2,3,3,3-tetrafluoropropene or 2-chloro-1,1,1,2-tetrafluoropropane, which is a precursor of 2,3,3,3-tetrafluoropropene, in two or three reaction steps, using at least one chlorine-containing compound selected from the group consisting of 1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene as a starting material, the reaction products of at least two of the steps being supplied to the same distillation apparatus to subject the products to a separation operation simultaneously. With this method, 2,3,3,3-tetrafluoropropene or 2-chloro-1,1,1,2-tetrafluoropropane, which is a precursor of 2,3,3,3-tetrafluoropropene, can be efficiently produced with reduced energy and equipment costs in an economically advantageous manner.

TECHNICAL FIELD

The present invention relates to a method for producing2,3,3,3-tetrafluoropropene.

BACKGROUND ART

Fluoroolefins represented by the formula: CF₃(CX₂)_(n)CF═CH₂, theformula: CF₃(CX₂)_(n)CH═CHF, and the like are useful compounds asvarious functional materials, solvents, refrigerants, blowing agents,and monomers for functional polymers or starting materials of suchmonomers. For example, fluoroolefins are used as monomers for modifyingethylene-tetrafluoroethylene copolymers. In particular, of thefluoroolefins mentioned above, 2,3,3,3-tetrafluoropropene (HFO-1234yf)represented by CF₃CF═CH₂ has recently gained attention because it offerspromising prospects as a refrigerant compound of low global-warmingpotential.

A known method for producing 2,3,3,3-tetrafluoropropene is a method inwhich halopropane or halopropene used as a starting material isfluorinated with hydrogen fluoride. For example, when1,1,1,2,3-pentachloropropane (HCC-240db) used as a starting material isfluorinated in a gas phase, the reactions proceed in the route asdescribed below.

CCl₃CHClCH₂Cl+3HF→CF₃CCl═CH₂+4HCl   (1)

CF₃CCl═CH₂+HF→CF₃CF═CH₂+HCl   (2)

In these reactions, the reaction rate in the reaction for producing2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) from1,1,1,2,3-pentachloropropane (first reaction) is significantly differentfrom that in the reaction for producing 2,3,3,3-tetrafluoropropene from2-chloro-3,3,3-trifluoropropene (second reaction). Thus, it isinefficient to perform these reactions using a single reactor, and it isideal to perform the reactions using separate reactors.

Further, regarding the second reaction, i.e., the step of producing2,3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene, amethod for producing 2,3,3,3-tetrafluoropropene in two reaction steps ofadding hydrogen fluoride to 2-chloro-3,3,3-trifluoropropene, and thenperforming a dehydrochlorination reaction, is known.

For example, Patent Literature 1 listed below discloses a method inwhich fluorination is performed using halopropane or halopropene as astarting material in a gas phase in three steps under conditionsaccording to each reaction, using three reactors containing differentcatalysts. Patent Literature 2 listed below discloses an integratedprocess using these reactions.

In these methods, however, it is difficult to obtain 100% conversion inthe reaction of each step, and it is necessary to separate the unreactedstarting materials and the target product from the reaction mixture torecycle the unreacted starting materials. Further, impurities, such ashydrogen chloride, contained in the reaction products tend to causecatalyst deterioration and a decrease in selectivity due to theoccurrence of a side reaction in the next step. Thus, after thecompletion of each step, unwanted substances, such as hydrogen chloride,are generally removed from the reaction mixture using a distillationcolumn, and components used as starting materials of the next step andthe unreacted starting materials are separated. Regarding a method forproducing 2,3,3,3-tetrafluoropropene using 1,1,1,2,3-pentachloropropane(HCC-240db) as a starting material in the two reaction steps describedabove, i.e., through the first reaction and the second reaction, FIG. 1shows a flow diagram of a conventional typical treatment process. Asshown in FIG. 1, the conventional method requires the following process:after the high-temperature reaction gases obtained in the firstreaction, which contains 2-chloro-3,3,3-trifluoropropene, are cooled andHCl is removed in a purification step, the components are heated againto allow a reaction to proceed at a high temperature in the step ofobtaining 2,3,3,3-tetrafluoropropene, and the gases obtained from theoutlet of the second reaction step is cooled again to obtain the desired2,3,3,3-tetrafluoropropene. Further, when unreacted1,1,1,2,3-pentachloropropane and intermediates, such as2-chloro-3,3,3-trifluoropropene, are recycled to the correspondingreaction steps, they must be reheated together with HF cooled in eachpurification step. As described above, the general production process,which requires repeated heating and cooling of the starting materialgases, intermediates, products, and the like, results in significantenergy loss and an increase in operating costs. The number ofdistillation columns required for separation is also increased, leadingto an increase in equipment costs.

CITATION LIST Patent Literature

PTL 1: WO2007/079431

PTL 2: JP2009-227675A

SUMMARY OF INVENTION Technical Problem

The present invention has been accomplished in view of the state of theart described above, and its primary object is to provide a method forproducing 2,3,3,3-tetrafluoropropene or2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), which is a precursorof 2,3,3,3-tetrafluoropropene, in two or three reaction steps, using atleast one chlorine-containing compound selected from the groupconsisting of 1,1,1,2,3-pentachloropropane (HCC-240db),2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), and1,1,2,3-tetrachloropropene (HCO-1230xa) as a starting material, in whichthe desired product can be efficiently produced with reduced energy andequipment costs in an economically advantageous manner.

Solution to Problem

The present inventors conducted extensive research to achieve the aboveobject, and found the following. Specifically, in the method forproducing 2,3,3,3-tetrafluoropropene or its precursor using theabove-mentioned specific chlorine-containing compounds as a startingmaterial in two or three reaction steps, when the products of theplurality of reaction steps are simultaneously subjected to distillationtreatment using the same distillation apparatus instead of conventionaldistillation treatment, which is performed using a separate distillationapparatus after the completion of each reaction step, the number ofdistillation apparatuses can be decreased to thus reduce equipmentcosts, and energy costs associated with heating and cooling can also bereduced, while sufficiently achieving the object of separating hydrogenchloride, the unreacted starting materials, intermediates, etc. Thepresent inventors further found that performing the reaction steps inparallel is very advantageous in terms of costs because it makes it easyto independently carry out each reaction step under optimum conditions,thus improving conversion and selectivity. The present inventorsconducted further extensive research based on these findings, andaccomplished the present invention.

More specifically, the present invention provides the following methodfor producing 2,3,3,3-tetrafluoropropene or2-chloro-1,1,1,2-tetrafluoropropane, which is a precursor of2,3,3,3-tetrafluoropropene.

-   Item 1. A method for producing 2,3,3,3-tetrafluoropropene,    comprising the reaction steps of:

(1) obtaining 2-chloro-3,3,3-trifluoropropene by reacting a fluorinatingagent with at least one chlorine-containing compound selected from thegroup consisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene; and

(2) obtaining 2,3,3,3-tetrafluoropropene by reacting the2-chloro-3,3,3-trifluoropropene with anhydrous hydrogen fluoride in agas phase in the presence of a fluorination catalyst while heating,

the method further comprising the step of supplying the products ofreaction step (1) and the products of reaction step (2) to the samedistillation apparatus to separate the products into a hydrogenchloride-containing fraction and a fraction substantially free ofhydrogen chloride.

Item 2. A method for producing 2,3,3,3-tetrafluoropropene, comprisingthe reaction steps of:

(1) obtaining 2-chloro-3,3,3-trifluoropropene by reacting a fluorinatingagent with at least one chlorine-containing compound selected from thegroup consisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene;

(2) obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to the 2-chloro-3,3,3-trifluoropropene; and

(3) obtaining 2,3,3,3-tetrafluoropropene by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane,

the method further comprising the step of supplying the products of twoor more of reaction steps (1) to (3) to the same distillation apparatusto separate the products into a hydrogen chloride-containing fractionand a fraction substantially free of hydrogen chloride.

-   Item 3. The method for producing 2,3,3,3-tetrafluoropropene    according to Item 1 or 2, wherein reaction step (1) is performed by    reacting anhydrous hydrogen fluoride with at least one    chlorine-containing compound selected from the group consisting of    1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane,    and 1,1,2,3-tetrachloropropene in a gas phase in the presence of a    fluorination catalyst while heating.-   Item.4. A method for producing 2,3,3,3-tetrafluoropropene,    comprising the reaction steps of:

(1) obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to 2-chloro-3,3,3-trifluoropropene; and

(2) obtaining 2,3,3,3-tetrafluoropropene by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane,

the method further comprising the step of supplying the products ofreaction step (1) and the products of reaction step (2) to the samedistillation apparatus to separate the products into a hydrogenchloride-containing fraction and a fraction substantially free ofhydrogen chloride.

-   Item 5. The method for producing 2,3,3,3-tetrafluoropropene    according to any one of Items 1 to 4, further comprising the step of    removing hydrogen chloride from the hydrogen chloride-containing    fraction.-   Item 6. The method for producing 2,3,3,3-tetrafluoropropene    according to Item 5, further comprising the step of recycling all or    part of the fraction from which hydrogen chloride has been removed    to at least one of the reaction steps.-   Item 7. The method for producing 2,3,3,3-tetrafluoropropene    according to any one of Items 1 to 6, further comprising the step of    collecting 2,3,3,3-tetrafluoropropene from the hydrogen    chloride-containing fraction and/or the fraction substantially free    of hydrogen chloride.-   Item 8. The method for producing 2,3,3,3-tetrafluoropropene    according to any one of Items 1 to 7, further comprising the step of    recycling all or part of the fraction substantially free of hydrogen    chloride to at least one of the reaction steps.-   Item 9. A method for producing 2-chloro-1,1,1,2-tetrafluoropropane,    comprising the reaction steps of:

(1) obtaining 2-chloro-3,3,3-trifluoropropene by reacting a fluorinatingagent with at least one chlorine-containing compound selected from thegroup consisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene; and

(2) obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to the 2-chloro-3,3,3-trifluoropropene,

the method further comprising the step of supplying the products ofreaction step (1) and the products of reaction step (2) to the samedistillation apparatus to separate the products into a hydrogenchloride-containing fraction and a fraction substantially free ofhydrogen chloride.

-   Item 10. The method for producing    2-chloro-1,1,1,2-tetrafluoropropane according to Item 9, wherein    reaction step (1) is performed by reacting anhydrous hydrogen    fluoride with at least one chlorine-containing compound selected    from the group consisting of 1,1,1,2,3-pentachloropropane,    2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene    in a gas phase in the presence of a fluorination catalyst while    heating.-   Item 11. The method for producing    2-chloro-1,1,1,2-tetrafluoropropane according to Item 9 or 10,    further comprising the step of removing hydrogen chloride from the    hydrogen chloride-containing fraction.-   Item 12. The method for producing    2-chloro-1,1,1,2-tetrafluoropropane according to Item 11, further    comprising the step of recycling all or part of the fraction from    which hydrogen chloride has been removed to at least one of the    reaction steps.-   Item 13. The method for producing    2-chloro-1,1,1,2-tetrafluoropropane according to any one of Items 9    to 12, further comprising the step of collecting    2-chloro-1,1,1,2-tetrafluoropropane from the hydrogen    chloride-containing fraction and/or the fraction substantially free    of hydrogen chloride.-   Item 14. The method for producing    2-chloro-1,1,1,2-tetrafluoropropane according to any one of Items 9    to 13, further comprising the step of recycling all or part of the    fraction substantially free of hydrogen chloride to at least one of    the reaction steps.

The method of the present invention is described in detail below.

(1) Features of the Method of the Present Invention

The method of the present invention produces 2,3,3,3-tetrafluoropropene(HFO-1234yf) or 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), whichis a precursor of 2,3,3,3-tetrafluoropropene, using at least onechlorine-containing compound selected from the group consisting of1,1,1,2,3-pentachloropropane (HCC-240db),2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), and1,1,2,3-tetrachloropropene (HCO-1230xa) as a starting material.

First, in the trifluoropropene-producing step of this method, thechlorine-containing compound used as a starting material is reacted witha fluorinating agent to produce 2-chloro-3,3,3-trifluoropropene.

Subsequently, in the tetrafluoropropene-producing procedure, the desired2,3,3,3-tetrafluoropropene is produced by fluorination of the2-chloro-3,3,3-trifluoropropene. The tetrafluoropropene-producingprocedure can be performed in a single reaction step in which2-chloro-3,3,3-trifluoropropene is reacted with anhydrous hydrogenfluoride in a gas phase to directly convert the2-chloro-3,3,3-trifluoropropene into 2,3,3,3-tetrafluoropropene, or intwo reaction steps in which hydrogen fluoride is added to2-chloro-3,3,3-trifluoropropene to obtain2-chloro-1,1,1,2-tetrafluoropropane and then 2,3,3,3-tetrafluoropropeneis obtained by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane.

In the method of the present invention, in which2,3,3,3-tetrafluoropropene or 2-chloro-1,1,1,2-tetrafluoropropane, whichis a precursor of 2,3,3,3-tetrafluoropropene, is produced in two orthree reaction steps, using the chlorine-containing compound describedabove as a starting material, the products of at least two of thereaction steps are supplied to the same distillation apparatus tosubject the products to a distillation operation simultaneously. Thismethod can reduce the number of distillation apparatuses that areconventionally used individually after each reaction step, and reduceapparatus costs. Further, since the reaction products of at least two ofthe reaction steps are subjected to a distillation operationsimultaneously, the number of cooling and subsequent heating operationsin the distillation step individually performed after each reaction stepcan be reduced, which is advantageous in terms of energy costs.Performing the reaction steps in parallel enables each reaction step tobe independently carried out under optimum conditions.

The method of the present invention having these features makes itpossible to efficiently obtain 2,3,3,3-tetrafluoropropene or2-chloro-1,1,1,2-tetrafluoropropane with reduced energy and equipmentcosts in an economically advantageous manner.

The trifluoropropene-producing step and tetrafluoropropene-producingprocedure of the present invention are described in detail below.

(1) Trifluoropropene-Producing Step

In the trifluoropropene-producing step, at least one chlorine-containingcompound selected from the group consisting of1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and1,1,2,3-tetrachloropropene is used as a starting material and reactedwith a fluorinating agent in the presence or absence of a catalyst toperform a fluorination reaction. Thereby,2-chloro-3,3,3-trifluoropropene can be obtained.

Examples of usable fluorinating agents include anhydrous hydrogenfluoride, fluorine, trifluoromethane, and the like. In particular,anhydrous hydrogen fluoride is preferred.

1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and1,1,2,3-tetrachloropropene used as starting materials are knowncompounds that can be easily obtained.

A method in which fluorination is performed by conducting a reactionusing anhydrous hydrogen fluoride in a gas phase in the presence of afluorination catalyst is described in detail below as an example of thetrifluoropropene-producing step.

Examples of usable fluorination catalysts include known catalysts thatare active in a fluorination reaction with hydrogen fluoride. Inparticular, it is preferable to use a chromium-atom-containingfluorination catalyst. By using such a catalyst and reacting thechlorine-containing compound and anhydrous hydrogen fluoride used asstarting materials according to the conditions described below,2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) can be obtained with highselectivity.

Examples of usable chromium-atom-containing fluorination catalystsinclude halides, oxides, and the like. Of these, examples of preferredcatalysts include CrCl₂, CrF₃, Cr₂O₃, CrO₂, CrO₃, and the like. Thesecatalysts may be supported on a carrier. There is no particularlimitation on the carrier, and examples of carriers include porousalumina silicates typified by zeolite, aluminum oxide, silicon oxide,activated carbon, titanium oxide, zirconium oxide, zinc oxide, aluminumfluoride, and the like.

In the present invention, it is particularly preferable to use at leastone catalyst selected from the group consisting of chromium oxide andfluorinated chromium oxide.

Among these catalysts, the chromium oxide, for instance, is notparticularly limited. For example, it is preferable to use chromiumoxide represented by the composition formula: CrO_(m), wherein m fallswithin the range of preferably 1.5<m<3, more preferably 2<m<2.75, andeven more preferably 2<m<2.3. Any chromium oxide catalysts in the formof powder, pellets, or the like may be used, as long as they aresuitable for the reaction. Of these, chromium oxide catalysts in theform of pellets are preferred. The above chromium oxide catalysts can beprepared, for example, by the method disclosed in JPH05-146680A.

In addition, the fluorinated chromium oxide can be prepared by themethod disclosed in JPH05-146680A. For example, it can be prepared byfluorinating the chromium oxide obtained by the above method withhydrogen fluoride (HF treatment).

The degree of fluorination is not particularly limited. For example,fluorinated chromium oxide having a fluorine content of about 10 toabout 45% by weight may be suitably used.

Further, a chromium-based catalyst as disclosed in JPH11-171806A mayalso be used as a chromium oxide catalyst or fluorinated chromium oxidecatalyst. The chromium-based catalyst comprises, as a main component, achromium compound containing at least one metallic element selected fromthe group consisting of the metallic elements disclosed inJPH11-171806A, i.e., indium, gallium, cobalt, nickel, zinc, andaluminum, and other metallic elements, i.e., vanadium, niobium, andindium. The chromium-based catalyst may be amorphous, partlycrystalline, or entirely crystalline.

The anhydrous hydrogen fluoride may be generally supplied to the reactortogether with the chlorine-containing compound used as a startingmaterial. The amount of anhydrous hydrogen fluoride is not particularlylimited. To achieve high selectivity of 2-chloro-3,3,3-trifluoropropene,the amount of anhydrous hydrogen fluoride is preferably about 3 mol ormore, and more preferably about 8 mol or more, per mol of thechlorine-containing compound used as a starting material. When theamount of anhydrous hydrogen fluoride is less than this range, theselectivity of 2-chloro-3,3,3-trifluoropropene and catalytic activitytend to undesirably decrease.

The upper limit of the amount of anhydrous hydrogen fluoride is notparticularly limited. An excessively large amount of hydrogen fluoridehas little influence on selectivity and conversion. However,productivity decreases because the amount of hydrogen fluoride to beseparated increases during purification. For this reason, the amount ofanhydrous hydrogen fluoride is generally preferably about 100 mol orless, and more preferably about 50 mol or less, per mol of thechlorine-containing compound used as a starting material.

A method in which a fluorination catalyst is placed into a tubular flowreactor, and the chlorine-containing compound and anhydrous hydrogenfluoride used as starting materials are introduced to the reactor can begiven as one specific embodiment of the method of the present invention.

The reactor is preferably made of a material resistant to the corrosiveaction of hydrogen fluoride, such as Hastelloy, Inconel, Monel, or thelike.

The lower limit of the reaction temperature is not particularly limitedbecause a lower reaction temperature is advantageous in terms of lessdecomposition of the starting materials and the products. However, ifthe temperature is too low, the conversion of the chlorine-containingcompound tends to decrease. For this reason, the reaction temperature ispreferably 200° C. or more, and more preferably 220° C. or more.

Regarding the upper limit of the reaction temperature, an excessivelyhigh reaction temperature is not preferable because an excessively highreaction temperature notably decreases catalytic activity due todecomposition of the starting materials, and easily causes formation ofC₁, C₂ compounds, and isomers, such as CF₃CH═CHF and CF₃CH═CHCl, asby-products. For this reason, the reaction temperature is preferablyabout 400° C. or less. In particular, the reaction temperature in thetrifluoropropene-producing reaction step is preferably about 200 toabout 380° C.

The pressure during the reaction is not particularly limited, and thereaction may be performed under reduced pressure, ordinary pressure, orincreased pressure. Although the reaction may be generally carried outat pressure near atmospheric pressure (0.1 MPa), it can also proceedsmoothly under reduced pressure of less than 0.1 MPa. Furthermore, thereaction may be performed under increased pressure within a range inwhich the starting materials do not liquefy.

There is no limitation on the contact time. For example, the contacttime, which is represented by W/F₀, is preferably adjusted to about 0.5to about 50 g·sec/mL, and more preferably about 1 to about 20 g·sec/mL.W/F₀ is the ratio of the catalyst amount W(g) to the total flow rate F₀(flow rate at 0° C., 0.1013 MPa: cc/sec) of the starting material gasessupplied to the reaction system.

The starting materials may be supplied to the reactor as is, or a gasthat is inert to the starting materials and catalyst, such as nitrogen,helium, or argon, may be present together with the starting materials.The concentration of the inert gas is about 0 to about 80 mol % based onthe amount of the gaseous components introduced into the reactor.

Further, when the reaction is performed in a gas phase in the presenceof a catalyst, one or both of oxygen and chlorine may be supplied to thereactor together with the starting materials to maintain catalyticactivity for a long period of time. This enables suppression of adecrease in catalytic activity.

The inert gas, oxygen, and/or chlorine may be added in either thetrifluoropropene-producing step or the below-describedtetrafluoropropene-producing procedure, or in both. When thetetrafluoropropene-producing procedure is performed in two steps, theinert gas, oxygen, and/or chlorine may be added in any of the hydrogenfluoride addition step and the dehydrochlorination step.

(2) Tetrafluoropropene-Producing Procedure

The tetrafluoropropene-producing procedure is a procedure for obtaining2,3,3,3-tetrafluoropropene or 2-chloro-1,1,1,2-tetrafluoropropane, whichis a precursor of 2,3,3,3-tetrafluoropropene, from the2-chloro-3,3,3-trifluoropropene obtained in thetrifluoropropene-producing step.

The reaction for obtaining 2,3,3,3-tetrafluoropropene from2-chloro-3,3,3-trifluoropropene can be performed by a method in which2-chloro-3,3,3-trifluoropropene is reacted with anhydrous hydrogenfluoride in a gas phase in the presence of a fluorination catalyst toobtain 2,3,3,3-tetrafluoropropene (single-step method); or a method inwhich hydrogen fluoride is added to 2-chloro-3,3,3-trifluoropropene toobtain 2-chloro-1,1,1,2-tetrafluoropropane, and2,3,3,3-tetrafluoropropene is obtained by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane (two-step method).

These methods are described in detail below.

(a) Single-Step Method

In the single-step method, 2-chloro-3,3,3-trifluoropropene is reactedwith anhydrous hydrogen fluoride in a gas phase in the presence of afluorination catalyst while heating to obtain 2,3,3,3-tetrafluoropropeneaccording to the following reaction formula.

CF₃CCl═CH₂+HF→CF₃CF═CH₂+HCl

The fluorination reaction in the tetrafluoropropene-producing reactionin the single-step method is performed in the presence of a fluorinationcatalyst. Examples of usable fluorination catalysts include knowncatalysts that are active in a fluorination reaction with hydrogenfluoride. For example, metal oxides and fluorinated metal oxides, suchas chromium oxide, fluorinated chromium oxide, aluminum oxide, andfluorinated aluminum oxide, can be used. Other examples of usablefluorination catalysts are metal fluorides, such as MgF₂, TaF₅, andSbF₅.

As chromium oxide and fluorinated chromium oxide among these, the samecatalysts as used in the trifluoropropene producing step described abovecan be used.

In the tetrafluoropropene-producing reaction procedure,2-chloro-3,3,3-trifluoropropene may be reacted with hydrogen fluoride(HF) in a gas phase in the presence of the fluorination catalystdescribed above while heating.

The specific reaction method is not particularly limited. When afraction, containing 2-chloro-3,3,3-trifluoropropene and anhydroushydrogen fluoride, separated in the distillation step described below iscirculated, the fraction may be further heated with a preheater togetherwith anhydrous hydrogen fluoride that is newly supplied as required, andsupplied to the reactor to allow a reaction to proceed in a gas phase.

The amount of hydrogen fluoride supplied in thetetrafluoropropene-producing reaction procedure is generally about 1 toabout 50 mol, preferably about 5 to about 30 mol, and more preferablyabout 7 to about 15 mol, per mol of 2-chloro-3,3,3-trifluoropropenesupplied to the reactor.

When the amount of hydrogen fluoride in the fraction, obtained in thedistillation step described below, that contains2-chloro-3,3,3-trifluoropropene is within the above range, afluorination reaction in the tetrafluoropropene-producing reactionprocedure can be performed by using only the products obtained in thedistillation step without adding further hydrogen fluoride. When theamount of hydrogen fluoride contained in the reaction products obtainedin the distillation step is larger than the above range, the reactionproducts may be used as starting materials for thetetrafluoropropene-producing reaction procedure after reducing theamount of hydrogen fluoride contained therein by a method such asdistillation.

The selectivity of 2,3,3,3-tetrafluoropropene can be maintained in adesirable range by using anhydrous hydrogen fluoride within the aboverange in the presence of the fluorination catalyst described above.

The form of the reactor used in the tetrafluoropropene-producingreaction procedure is not particularly limited.

Examples of usable reactors include adiabatic reactors containing acatalyst, multitubular reactors cooled using a heating medium, and thelike. The reactor is preferably made of a material resistant to thecorrosive action of hydrogen fluoride, such as Hastelloy, Inconel,Monel, or the like.

The reaction temperature, i.e., the temperature in the reactor, isgenerally about 200 to about 500° C., preferably about 300 to about 450°C., and more preferably about 350 to about 400° C. If the reactiontemperature is higher than this range, the selectivity of2,3,3,3-tetrafluoropropene undesirably decreases. If the reactiontemperature is lower than this range, the conversion of the startingcompound undesirably decreases.

The pressure during the reaction is not particularly limited, and thereaction may be performed under ordinary pressure or increased pressure.More specifically, the reaction in the present invention may beperformed under atmospheric pressure (0.1 MPa), and may also beperformed under an increased pressure of up to about 1.0 MPa.

The reaction time is not particularly limited. However, the contacttime, which is represented by W/F₀, may be generally adjusted to therange of about 5 to about 20 g·sec/cc. W/Fo is the ratio of the catalystamount W(g) to the total flow rate Fo (flow rate at 0° C., 0.1013 MPa:cc/sec) of the starting material gases supplied (total amount of2-chloro-3,3,3-trifluoropropene and HF).

(b) Two-Step Method

(i) In the first step of the two-step method, hydrogen fluoride is addedto 2-chloro-3,3,3-trifluoropropene to produce2⁻chloro-1,1,1,2-tetrafluoropropane.

Various methods for producing 2-chloro-1,1,1,2-tetrafluoropropane byadding hydrogen fluoride to 2-chloro-3,3,3-trifluoropropene are known(WO2011/56441, WO2009/018561, and the like). In the present invention,these known methods can be appropriately applied.

For example, hydrogen fluoride can be added to2-chloro-3,3,3-trifluoropropene in a liquid phase to produce2-chloro-1,1,1,2-tetrafluoropropane. This method can be performed bysupplying 2-chloro-3,3,3-trifluoropropene together with an excess ofhydrogen fluoride to a liquid phase reactor containing a hydrogenfluoride addition catalyst such as SbCl₃, SbCl₅, SbF₅, or the like. Asthe reaction conditions, known conditions may be appropriately applied.For example, the reaction temperature may be about 85° C.

A known method for producing 2-chloro-1,1,1,2-tetrafluoropropane byadding hydrogen fluoride to 2-chloro-3,3,3-trifluoropropene through agas phase reaction is, for example, a method in which2-chloro-3,3,3-trifluoropropene and an excess of hydrogen fluoride areallowed to pass through a reactor containing a SbCl₅ catalyst supportedon carbon. Other examples of catalysts that can be used in the hydrogenfluoride addition reaction in a gas phase include chromium-basedcatalysts, such as chromium oxide and fluorinated chromium oxide. As thereaction conditions of the gas phase reaction, known conditions may beappropriately applied. For example, the reaction temperature may bewithin the range of about 50 to about 300° C.

In view of the apparatus configuration of the process, controllability,and the like, the reaction of addition of hydrogen fluoride to2-chloro-3,3,3-trifluoropropene is preferably performed through a gasphase reaction.

2-chloro-1,1,1,2-tetrafluoropropane can be obtained by performing theabove-described hydrogen fluoride addition reaction in the first step.Since 2-chloro-1,1,1,2-tetrafluoropropane can be converted into2,3,3,3-tetrafluoropropene by performing the below-describeddehydrochlorination reaction in the second step, it is a useful compoundas a precursor of 2,3,3,3-tetrafluoropropene. Therefore, the reactionuntil the completion of the hydrogen fluoride addition in the first stepcan be defined as a method for producing2-chloro-1,1,1,2-tetrafluoropropane.

Although the products of the first step do not contain hydrogenchloride, they are generally subjected to a distillation operation toseparate useful materials and impurities from the products.

(ii) In the reaction of the second step, 2,3,3,3-tetrafluoropropene canbe obtained by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane.

Various methods for dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane are known (WO2011/56441,WO2009/018561, and the like). In the present invention, these knownmethods can be appropriately applied.

For example, the dehydrochlorination reaction can be performed bysupplying 2-chloro-1,1,1,2-tetrafluoropropane to a basic aqueoussolution. Examples of basic aqueous solutions include aqueous NaOHsolution, aqueous KOH solution, and the like. As the specific reactionconditions, known conditions may be appropriately applied.

As for dehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropanethrough a gas phase reaction, the method disclosed in WO2009/018561, forexample, can be applied. This method can be performed by, for example,bringing 2-chloro-1,1,1,2-tetrafluoropropane into contact with adehydrochlorination catalyst. Examples of catalysts include metalhalides on carbon and/or metal, halogenated metal oxides on carbonand/or metal, and the like. As the reaction conditions of the gas phasereaction, known conditions may be appropriately applied. The reactiontemperature may be within the range of, for example, about 200 to about550° C.

In view of the apparatus configuration of the process, controllability,and the like, the dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane is preferably performed through agas phase reaction.

(3) Distillation Step

(i) In the method described above, in which thetrifluoropropene-producing reaction and the tetrafluoropropene-producingreaction are performed, when the tetrafluoropropene-producing reactionis performed by the single-step method, 2,3,3,3-tetrafluoropropene canbe obtained from the chlorine-containing compound as a starting materialin two steps. When the tetrafluoropropene-producing reaction isperformed by the two-step method, 2,3,3,3-tetrafluoropropene can beobtained from the chlorine-containing compound as a starting material inthree steps.

In the method for producing 2,3,3,3-tetrafluoropropene of the presentinvention, which comprises these two steps or three steps, the reactionproducts of at least two of the steps are supplied to the samedistillation apparatus to subject the reaction products to a separationoperation simultaneously. In particular, in the method comprising threesteps, the reaction products of all of the steps are preferably suppliedto the same distillation apparatus to subject the products to adistillation operation simultaneously.

When the products of each reaction step are supplied to the distillationapparatus, the components obtained from the outlets of the reactionsteps may be mixed before they are supplied to the distillationapparatus, or the components obtained from the outlets of the reactionsteps may be separately introduced into the distillation apparatus fromdifferent desired positions, for example, separately introduced from amiddle portion of the distillation column, the bottom of thedistillation column, etc. When they are introduced from differentpositions of the distillation apparatus, the positions from which theyare introduced are appropriately determined according to the compositionof the components obtained from the outlet of each reaction step and thecomposition of each fraction obtained from the separation step.

When the reaction before supplying to the distillation step is a gasphase reaction, the components obtained from the outlet of the reactorcan be supplied as is to the distillation step. When the reaction beforesupplying to the distillation step is a liquid phase reaction, volatilecomponents can be continuously removed from the reactor and supplied tothe distillation step. When the liquid phase portion is continuouslyremoved and supplied to the separation step, a step of removing andcollecting the catalyst contained in the liquid phase portion may beperformed as a pretreatment step before the distillation step.

The distillation conditions in the distillation step may be conditionsunder which the products can be separated into a hydrogenchloride-containing fraction and a fraction substantially free ofhydrogen chloride. In this case, to almost completely remove hydrogenchloride contained in the reaction products, the hydrogenchloride-containing fraction preferably contains substantially the sameamount of hydrogen chloride as the amount of hydrogen chlorideintroduced into the distillation step.

If necessary, the hydrogen chloride-free fraction separated in thedistillation step may be further subjected to a crude purificationtreatment step (separation step), such as distillation, to separate theunreacted starting materials usable in the reaction steps,intermediates, hydrogen fluoride, and the like, after which these may beindividually recycled to any of the reaction steps.

After the hydrogen chloride-containing fraction is subjected to a stepof removing hydrogen chloride, it may also be subjected to a separationstep to separate the unreacted starting materials usable in the reactionsteps, intermediates, hydrogen fluoride, and the like, after which thesemay be individually recycled to any of the reaction steps.

Examples of intermediates as used herein include compounds produced as aresult of reactions such as replacement of chlorine atom(s) of thestarting material chlorine-containing compound by fluorine, hydrogenfluoride addition, dehydrochlorination, or dehydrofluorination. Althoughthey depend on the step used and the reaction conditions thereof,specific examples include 1,1,2,3-tetrachloro-1-fluoropropane(HCFC-241db), 1,1,2-trichloro-1,3-difluoropropane (HCFC-242dc),2,3,3-trichloro-3-fluoropropene (HCFO-1231xf),2,3-dichloro-3,3-difluoropropene (HCFO-1232xf),1,1,1,2,2-pentafluoropropane (HFC-245cb), and the like.

When the desired 2,3,3,3-tetrafluoropropene is contained in the hydrogenchloride-containing fraction and/or the fraction free of hydrogenchloride, the hydrogen chloride-containing fraction and/or the fractionfree of hydrogen chloride may be subjected to a step of collecting2,3,3,3-tetrafluoropropene, and the components other than2,3,3,3-tetrafluoropropene can be recycled to necessary steps.

When the fractions obtained in the distillation step are recycled, anacid removal step, a moisture removal step, a crude purification step,such as distillation, or the like may be performed if necessary. Thetreatment conditions of each step may be appropriately set depending onthe components to be separated.

For example, in the method for producing 2,3,3,3-tetrafluoropropenecomprising two steps, specific distillation conditions in thedistillation step may be conditions under which2-chloro-3,3,3-trifluoropropene, hydrogen fluoride, and the like can beseparated as high-boiling-point components, and2,3,3,3-tetrafluoropropene, hydrogen chloride, and the like can beseparated as low-boiling-point components. Of the fractions thusseparated, the fraction containing 2-chloro-3,3,3-trifluoropropene,hydrogen fluoride, and the like, which are high-boiling-pointcomponents, may further be, if necessary, subjected to distillationtreatment or the like to separate 2-chloro-3,3,3-trifluoropropene,1,1,1,2,2-pentafluoropropane, which is an intermediate of2-chloro-3,3,3-trifluoropropene, hydrogen fluoride, and the like. Thesecomponents can be used as starting materials in thetetrafluoropropene-producing procedure. Hydrogen fluoride contained inan excess amount can be recycled, for example, as a starting material inthe trifluoropropene-producing step.

The fraction containing 2,3,3,3-tetrafluoropropene, hydrogen chloride,and the like separated as low-boiling-point components can further besubjected to any purification step such as single- or multi-stagedistillation, liquid separation, extraction, or extractive distillation,to separate and collect 2,3,3,3-tetrafluoropropene. For example, when adistillation operation is performed as a separation means, a single- ormulti-stage distillation operation can be carried out to collecthigh-purity 2,3,3,3-tetrafluoropropene from the bottom of the finaldistillation column or a middle portion of the final distillationcolumn. Hydrogen chloride can be collected from the top of thedistillation column and recycled for the desired purpose. Other organiccomponents contained in the hydrogen chloride-containing fraction arechlorine-containing fluorides, which can be used as intermediatematerials in the reaction steps. Thus, these organic components can beseparated in the step of collecting 2,3,3,3-tetrafluoropropene andrecycled to the desired reaction steps.

(ii) When the tetrafluoropropene-producing procedure is performed by thetwo-step method, i.e., when hydrogen fluoride is added to2-chloro-3,3,3-trifluoropropene to obtain2-chloro-1,1,1,2-tetrafluoropropane, and then a dehydrochlorinationreaction is performed to obtain 2,3,3,3-tetrafluoropropene, thereactions of the two steps can be used as a method for producing2,3,3,3-tetrafluoropropene. In this case, as2-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropeneobtained as a product of the trifluoropropene-producing step describedabove or 2-chloro-3,3,3-trifluoropropene obtained by any other methodmay be used.

In this method, the reaction products of the step of addition ofhydrogen fluoride to 2-chloro-3,3,3-trifluoropropene and the reactionproducts of the step of dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane may be introduced into the samedistillation apparatus to perform a distillation operationsimultaneously. This method makes it possible to simultaneously performcollection of useful materials from the reaction products of the step ofaddition of hydrogen fluoride as well as removal of hydrogen chlorideand collection of useful materials from the reaction products of thedehydrochlorination step by using a single distillation apparatus. Alsoin this case, the unreacted starting materials, intermediates, hydrogenfluoride, and the like contained in each fraction can be, if necessary,recycled to any of the steps after being subjected to a separation step.(iii) As stated above, in the tetrafluoropropene-producing procedureperformed in two reaction steps, 2-chloro-1,1,1,2-tetrafluoropropane,which is useful as a precursor of 2,3,3,3-tetrafluoropropene, can beobtained by performing the hydrogen fluoride addition reaction in thefirst step.

Thus, the method in which 2-chloro-3,3,3-trifluoropropene is obtainedthrough the trifluoropropene-producing step, and then hydrogen fluorideis added to the obtained 2-chloro-3,3,3-trifluoropropene is useful as amethod for producing 2-chloro-1,1,1,2-tetrafluoropropane.

Also in this method, the reaction products of thetrifluoropropene-producing step and the reaction products of thehydrogen fluoride addition step may be introduced into the samedistillation apparatus to perform a distillation operationsimultaneously. Thereby, the method makes it possible to simultaneouslyperform removal of hydrogen chloride from the products of thetrifluoropropene-producing step and collection of useful components byusing a single distillation apparatus. Also in this case, the unreactedstarting materials, intermediates, hydrogen fluoride, and the likecontained in each fraction may be, if necessary, recycled to any of thesteps after being subjected to a separation step.

ADVANTAGEOUS EFFECTS OF INVENTION

The method of the present invention makes it possible to efficientlyproduce 2,3,3,3-tetrafluoropropene or2-chloro-1,1,1,2-tetrafluoropropane, which is a precursor of2,3,3,3-tetrafluoropropene, using at least one chlorine-containingcompound selected from the group consisting of1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and1,1,2,3-tetrachloropropene as a starting material, with reduced energyand equipment costs in an economically advantageous manner.

Further, the present invention also makes it possible to perform amethod for producing 2,3,3,3-tetrafluoropropene by adding hydrogenfluoride to 2-chloro-3,3,3-trifluoropropene to obtain2-chloro-1,1,1,2-tetrafluoropropane and then conducting adehydrochlorination reaction, with reduced energy and equipment costs inan economically advantageous manner.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows a flow diagram of the general reaction process used inComparative Example 1 for producing 2,3,3,3-tetrafluoropropene using in1,1,1,2,3-pentachloropropane as a starting material.

FIG. 2 is a flow diagram of the reaction process in Examples 1 to 3.

FIG. 3 is a flow diagram of the reaction process in Examples 4 and 5.

DESCRIPTION OF EMBODIMENTS

The present invention is described in more detail below with referenceto Examples.

Example 1

According to the flow diagram shown in FIG. 2,2,3,3,3-tetrafluoropropene was produced using1,1,1,2,3-pentachloropropane as a starting material by a processcomprising the trifluoropropene-producing step and thetetrafluoropropene-producing procedure (single-step method).

A Hastelloy reactor with a capacity of 1.5 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 1.3 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 9 L was used as areactor for the tetrafluoropropene-producing procedure (reactor 2), and7.7 kg of chromium oxide containing CrO₂ as a main component was placedin the reactor as a catalyst.

As a pretreatment before the use of these catalysts for thecorresponding reactions, fluorination treatment was performed by passinganhydrous hydrogen fluoride diluted with nitrogen through the reactorsand raising the temperature of each reactor from 200° C. to 360° C. Thefluorinated catalysts were used for the corresponding reactions withoutbeing removed.

While allowing nitrogen to flow into the reactors, the reactors andpreheaters were each heated with an electric furnace.

After predetermined temperatures were reached, an operation of theprocess shown in FIG. 2 started.

The operating conditions of the reactor for thetrifluoropropene-producing reaction step (reactor 1) were as follows: apressure of 0.1 MPa and a temperature of 300° C. The operatingconditions of the reactor for the tetrafluoropropene-producing reactionprocedure (reactor 2) were as follows: a pressure of 0.1 MPa and atemperature of 365° C. The operating conditions of distillation column 1(HCl separation step) were as follows: a pressure of 0.75 MPa, a columntop temperature of −13° C., and a column bottom temperature of 92° C.Further, a distillation operation at a pressure of 0.75 MPa, a columntop temperature of 87° C., and a column bottom temperature of 90° C. wasperformed using distillation column 2 as a crude purification step. 50hours after the operation of the process started, the composition ofcomponents in each step of the reaction process was analyzed using gaschromatography. Table 1 shows the operating conditions of each step ofthe reaction process. Table 2 shows the results of the analysis. Thecircled numbers shown in Table 2 correspond to the numbers of the stepsof the reaction process shown in FIG. 2.

The structure of each product is as follows:

-   CF₃CF═CH₂ (HFO-1234yf)-   CF₃CF₂CH₃ (HFC-245cb)-   CF₃CCl═CH₂ (HCFO-1233xf)-   CCl₃CHClCH₂Cl (HCC-240db)

TABLE 1 Reaction Temperature Pressure Reaction Step (° C.) (MPa) Reactor1 300 0.1 Reactor 2 365 0.1 Column Top Column Bottom TemperatureTemperature Pressure Distillation Step (° C.) (° C.) (MPa) Distillation−13 92 0.75 Column 1 (HCl Separation) Distillation 87 90 0.75 Column 2(Crude Purification)

TABLE 2 O₂ HCl HF 1234yf 245cb 1233xf 240db (kmol/hr) (kmol/hr)(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) {circle around (1)}0.00 0.00 4.50 0.00 0.00 0.00 1.14 {circle around (2)} 0.00 0.00 23.90.00 0.00 0.08 1.14 {circle around (3)} 0.00 4.52 20.5 0.00 0.00 1.210.01 {circle around (4)} 1.02 0.00 0.00 0.00 0.00 0.00 0.00 {circlearound (5)} 1.02 0.00 145 0.01 0.34 7.14 0.00 {circle around (6)} 1.021.13 144 1.13 0.34 6.01 0.00 {circle around (7)} 1.02 5.65 164 1.13 0.347.22 0.01 {circle around (8)} 1.02 5.65 0.00 1.12 0.00 0.00 0.00 {circlearound (9)} 0.00 0.00 164 0.01 0.34 7.22 0.00 {circle around (10)}  0.000.00 145 0.01 0.34 7.14 0.00 {circle around (11)}  0.00 0.00 19.4 0.000.00 0.08 0.01

As is clear from Table 2, it can be confirmed that separation ofhydrogen chloride and collection of 2,3,3,3-tetrafluoropropene from theproducts can be carried out using a single distillation apparatus bysupplying the components obtained from the outlet of the reactor for thetrifluoropropene-producing reaction step (reactor 1) and the componentsobtained from the outlet of the reactor for thetetrafluoropropene-producing reaction procedure (reactor 2) to the samedistillation apparatus to perform a distillation operation. Further, theresults show that the unreacted starting material, intermediates,hydrogen fluoride, and the like can effectively be used by subjectingthe fraction free of hydrogen chloride to a crude purification(distillation) operation.

Example 2

According to the flow diagram shown in FIG. 2,2,3,3,3-tetrafluoropropene was produced using2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) as a starting materialby a process comprising the trifluoropropene-producing step and thetetrafluoropropene-producing procedure (single-step method).

A Hastelloy reactor with a capacity of 1.3 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 1.1 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 12 L was used as areactor for the tetrafluoropropene-producing procedure (reactor 2), and10 kg of chromium oxide containing CrO₂ as a main component was placedin the reactor as a catalyst.

Fluorination treatment of the catalysts before the reactions and heatingof the reactors were performed in the same manner as in Example 1.Thereafter, an operation of the process started under the operatingconditions shown in Table 3. The composition of components in each stepof the reaction process was analyzed using gas chromatography in thesame manner as in Example 1. Table 4 shows the results.

TABLE 3 Reaction Temperature Pressure Reaction Step (° C.) (MPa) Reactor1 300 0.1 Reactor 2 365 0.1 Column Top Column Bottom TemperatureTemperature Pressure Distillation Step (° C.) (° C.) (MPa) Distillation−1.4 92 0.75 Column 1 (HCl Separation) Distillation 86 88 0.75 Column 2(Crude Purification)

TABLE 4 O₂ HCl HF 1234yf 245cb 1233xf 243db (kmol/hr) (kmol/hr)(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) {circle around (1)}0.00 0.00 1.50 0.00 0.00 0.00 1.82 {circle around (2)} 0.00 0.00 19.60.00 0.00 0.13 1.82 {circle around (3)} 0.00 1.82 19.6 0.00 0.00 1.940.01 {circle around (4)} 1.02 0.00 0.00 0.00 0.00 0.00 0.00 {circlearound (5)} 1.02 0.00 134 0.01 0.46 11.4 0.00 {circle around (6)} 1.021.82 132 1.83 0.46 9.55 0.00 {circle around (7)} 1.02 3.64 152 1.83 0.4611.5 0.01 {circle around (8)} 1.02 3.64 0.00 1.82 0.00 0.00 0.00 {circlearound (9)} 0.00 0.00 152 0.01 0.46 11.5 0.01 {circle around (10)}  0.000.00 134 0.01 0.46 11.4 0.00 {circle around (11)}  0.00 0.00 18.1 0.000.00 0.13 0.01

As is clear from Table 4, also when 2,3-dichloro-1,1,1-trifluoropropaneis used as a starting material, it can be confirmed that separation ofhydrogen chloride and collection of 2,3,3,3-tetrafluoropropene from theproducts can be carried out using a single distillation apparatus bysupplying the components obtained from the outlet of the reactor for thetrifluoropropene-producing reaction step (reactor 1) and the componentsobtained from the outlet of the reactor for thetetrafluoropropene-producing reaction procedure (reactor 2) to the samedistillation apparatus to perform a distillation operation. Further, theresults show that the unreacted starting material, intermediates,hydrogen fluoride, and the like can effectively be used by subjectingthe fraction free of hydrogen chloride to a crude purification(distillation) operation.

Example 3

According to the flow diagram shown in FIG. 2,2,3,3,3-tetrafluoropropene was produced using 1,1,2,3-tetrachloropropeneas a starting material by a process comprising thetrifluoropropene-producing step and the tetrafluoropropene-producingprocedure (single-step method).

A Hastelloy reactor with a capacity of 1.3 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 1.1 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 7.7 L was used as areactor for the tetrafluoropropene-producing procedure (reactor 2), and6.4 kg of chromium oxide containing CrO₂ as a main component was placedin the reactor as a catalyst.

Fluorination treatment of the catalysts before the reactions and heatingof the reactors were performed in the same manner as in Example 1.Thereafter, an operation of the process started under the operatingconditions shown in Table 5. The composition of components in each stepof the reaction process was analyzed using gas chromatography in thesame manner as in Example 1. Table 6 shows the results.

TABLE 5 Reaction Temperature Pressure Reaction Step (° C.) (MPa) Reactor1 300 0.1 Reactor 2 365 0.1 Column Top Column Bottom TemperatureTemperature Pressure Distillation Step (° C.) (° C.) (MPa) Distillation−8.9 92 0.75 Column 1 (HCl Separation) Distillation 88 89 0.75 Column 2(Crude Purification)

TABLE 6 O₂ HCl HF 1234yf 245cb 1233xf 1230xa (kmol/hr) (kmol/hr)(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) {circle around (1)}0.00 0.00 7.00 0.00 0.00 0.00 1.82 {circle around (2)} 0.00 0.00 27.20.00 0.00 0.13 1.82 {circle around (3)} 0.00 5.43 21.8 0.00 0.00 1.940.01 {circle around (4)} 1.02 0.00 0.00 0.00 0.00 0.00 0.00 {circlearound (5)} 1.02 0.00 167 0.01 0.46 11.4 0.00 {circle around (6)} 1.021.82 165 1.83 0.46 9.55 0.00 {circle around (7)} 1.02 7.25 187 1.83 0.4611.5 0.01 {circle around (8)} 1.02 7.25 0.00 1.82 0.00 0.00 0.00 {circlearound (9)} 0.00 0.00 187 0.01 0.46 11.5 0.01 {circle around (10)}  0.000.00 167 0.01 0.46 11.4 0.00 {circle around (11)}  0.00 0.00 20.2 0.000.00 0.13 0.01

As is clear from Table 6, also when 1,1,2,3-tetrachloropropene is usedas a starting material, it can be confirmed that separation of hydrogenchloride and collection of 2,3,3,3-tetrafluoropropene from the productscan be carried out using a single distillation apparatus by supplyingthe components obtained from the outlet of the reactor for thetrifluoropropene-producing reaction step (reactor 1) and the componentsobtained from the outlet of the reactor for thetetrafluoropropene-producing reaction procedure (reactor 2) to the samedistillation apparatus to perform a distillation operation. Further, theresults show that the unreacted starting material, intermediates,hydrogen fluoride, and the like can effectively be used by subjectingthe fraction free of hydrogen chloride to a crude purification(distillation) operation.

Example 4

According to the flow diagram shown in FIG. 3,2,3,3,3-tetrafluoropropene was produced by a process comprising thetrifluoropropene-producing step in which 2-chloro-3,3,3-trifluoropropeneis obtained using 1,1,2,3-tetrachloropropene as a starting material, andcomprising the tetrafluoropropene-producing procedure performed in tworeaction steps in which hydrogen fluoride is added to the2-chloro-3,3,3-trifluoropropene obtained in thetrifluoropropene-producing step to produce2-chloro-1,1,1,2-tetrafluoropropane and then a dehydrochlorinationreaction is performed to produce 2,3,3,3-tetrafluoropropene.

A Hastelloy reactor with a capacity of 0.5 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 0.4 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 2.5 L was used as areactor for the step of addition of hydrogen fluoride to2-chloro-3,3,3-trifluoropropene (reactor 2), and 2.1 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 2.0 L was used as areactor for the step of dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane (reactor 3), and 1.6 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst.

Fluorination treatment of the catalysts before the reactions and heatingof the reactors were performed in the same manner as in Example 1.Thereafter, an operation of the process started under the operatingconditions shown in Table 7. The composition of components in each stepof the reaction process was analyzed using gas chromatography in thesame manner as in Example 1. Table 8 shows the results.

TABLE 7 Reaction Temperature Pressure Reaction Step (° C.) (MPa) Reactor1 300 0.1 Reactor 2 365 0.1 Reactor 3 365 0.1 Column Top Column BottomTemperature Temperature Pressure Distillation Step (° C.) (° C.) (MPa)Distillation −1.8 92 0.75 Column 1 (HCl Separation) Distillation 84 960.75 Column 2 (Crude Purification)

TABLE 8 HF 1233xf 244bb HCl (kmol/ 1234yf (kmol/ 1230xa (kmol/ (kmol/hr)hr) (kmol/hr) hr) (kmol/hr) hr) {circle around (1)} 0.00 9.00 0.00 0.002.97 0.00 {circle around (2)} 8.91 0.09 0.00 2.97 0.00 0.00 {circlearound (3)} 0.00 2.70 0.00 0.00 0.00 0.00 {circle around (4)} 0.00 12.60.02 14.3 0.00 9.66 {circle around (5)} 0.00 0.00 0.02 1.66 0.00 22.3{circle around (6)} 0.00 9.50 0.00 0.00 0.00 13.6 {circle around (7)}2.85 19.3 2.85 9.80 0.00 0.95 {circle around (8)} 11.8 19.4 2.88 14.30.00 23.3 {circle around (9)} 0.00 19.4 0.02 14.3 0.00 23.3 {circlearound (10)}  11.8 0.00 2.86 0.00 0.00 0.00 {circle around (11)}  0.009.90 0.02 14.3 0.00 9.66

As is clear from Table 8, also in the method comprising three steps inwhich the tetrafluoropropene-producing reaction procedure is performedin two steps, it can be confirmed that separation of hydrogen chlorideand collection of 2,3,3,3-tetrafluoropropene from the products can becarried out using a single distillation apparatus by supplying thecomponents obtained from the outlet of the reactor for thetrifluoropropene-producing reaction step (reactor 1), the componentsobtained from the outlet of the reactor for the step of addition ofhydrogen fluoride to 2-chloro-3,3,3-trifluoropropene (reactor 2), andthe components obtained from the outlet of the reactor for the step ofdehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropane (reactor 3)to the same distillation apparatus to perform a distillation operation.Further, the results show that the unreacted starting material,intermediates, hydrogen fluoride, and the like can effectively be usedby subjecting the fraction free of hydrogen chloride to a crudepurification (distillation) operation.

Example 5

According to the flow diagram shown in FIG. 3,2,3,3,3-tetrafluoropropene was produced using2,3-dichloro-1,1,1-trifluoropropane as a starting material. Thetetrafluoropropene-producing procedure was carried out in the samemanner as in Example 4 in two steps in which hydrogen fluoride is addedto the 2-chloro-3,3,3-trifluoropropene obtained in thetrifluoropropene-producing step to produce2-chloro-1,1,1,2-tetrafluoropropane, and then a dehydrochlorinationreaction is performed to produce 2,3,3,3-tetrafluoropropene.

A Hastelloy reactor with a capacity of 0.12 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 0.1 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 1.7 L was used as areactor for the step of addition of hydrogen fluoride to2-chloro-3,3,3-trifluoropropene (reactor 2), and 1.4 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst. A Hastelloy reactor with a capacity of 1.7 L was used as areactor for the step of dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane (reactor 3), and 1.4 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst.

Fluorination treatment of the catalysts before the reactions and heatingof the reactors were performed in the same manner as in Example 1.Thereafter, an operation of the process started under the operatingconditions shown in Table 9. The composition of components in each stepof the reaction process was analyzed using gas chromatography in thesame manner as in Example 1. Table 10 shows the results.

TABLE 9 Reaction Temperature Pressure Reaction Step (° C.) (MPa) Reactor1 300 0.1 Reactor 2 365 0.1 Reactor 3 365 0.1 Column Top Column BottomTemperature Temperature Pressure Distillation Step (° C.) (° C.) (MPa)Distillation 8.3 92 0.75 Column 1 (HCl Separation) Distillation 86 960.75 Column 2 (Crude Purification)

TABLE 10 HF 1233xf 243db HCl (kmol/ 1234yf (kmol/ 244bb (kmol/ (kmol/hr)hr) (kmol/hr) hr) (kmol/hr) hr) {circle around (1)} 0.00 0.00 0.00 0.000.00 3.00 {circle around (2)} 3.00 0.00 0.00 3.00 0.00 0.00 {circlearound (3)} 0.00 2.60 0.00 0.00 0.00 0.00 {circle around (4)} 0.00 13.00.03 12.5 11.7 0.00 {circle around (5)} 0.00 0.50 0.03 0.00 24.2 0.00{circle around (6)} 0.00 10.2 0.00 0.00 13.4 0.00 {circle around (7)}2.82 19.9 2.80 9.70 0.90 0.00 {circle around (8)} 5.82 20.4 2.83 12.725.1 0.00 {circle around (9)} 0.00 20.6 0.03 12.5 25.1 0.00 {circlearound (10)}  5.82 0.02 2.80 0.20 0.00 0.00 {circle around (11)}  0.0010.4 0.03 12.5 11.7 0.00

As is clear from Table 10, also in the method for producing2,3,3,3-tetrafluoropropene using 2,3-dichloro-1,1,1-trifluoropropane asa starting material in three steps in which thetetrafluoropropene-producing reaction procedure is performed in twosteps, it can be confirmed that separation of hydrogen chloride andcollection of 2,3,3,3-tetrafluoropropene from the products can becarried out using a single distillation apparatus by supplying thecomponents obtained from the outlet of the reactor for thetrifluoropropene-producing reaction step (reactor 1), the componentsobtained from the outlet of the reactor for the step of addition ofhydrogen fluoride to 2-chloro-3,3,3-trifluoropropene (reactor 2), andthe components obtained from the outlet of the reactor for the step ofdehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropane (reactor 3)to the same distillation apparatus to perform a distillation operation.Further, the results show that the unreacted starting material,intermediates, hydrogen fluoride, and the like can effectively be usedby subjecting the fraction free of hydrogen chloride to a crudepurification (distillation) operation.

Comparative Example 1

As a comparative example, 2,3,3,3-tetrafluoropropene was produced using1,1,1,2,3-pentachloropropane as a starting material by the generalprocess shown in FIG. 1.

More specifically, after the trifluoropropene-producing step in which2-chloro-3,3,3-trifluoropropene is obtained using1,1,1,2,3-pentachloropropane as a starting material was performed inreactor 1, a distillation operation for separating HCl, which is aby-product, was carried out in a distillation column A. Subsequently, adistillation operation for separating unreacted1,1,1,2,3-pentachloropropane and 2-chloro-3,3,3-trifluoropropene, whichis a reaction product, was performed using a distillation column B as acrude purification step. The tetrafluoropropene-producing procedure inwhich 2-chloro-3,3,3-trifluoropropene is fluorinated to produce2,3,3,3-tetrafluoropropene was then performed in reactor 2. Thecomponents obtained from the outlet of the reactor of thetetrafluoropropene-producing procedure was supplied to a distillationcolumn C, and a distillation operation was carried out to separate thecomponents into a column top fraction containing HCl and2,3,3,3-tetrafluoropropene as main components, and a column bottomfraction containing HF and 2-chloro-3,3,3-trifluoropropene as maincomponents. The column bottom fraction was recycled to the reactor 2.The column top fraction can be subjected to any purification step toobtain 2,3,3,3-tetrafluoropropene.

A Hastelloy reactor with a capacity of 1.2 L was used as a reactor forthe trifluoropropene-producing step (reactor 1), and 1.0 kg of chromiumoxide containing CrO₂ as a main component was placed in the reactor as acatalyst.

The operating conditions in the distillation column A (HCl separationstep) were as follows: a pressure of 0.75 MPa, a column top temperatureof −31° C., and a column bottom temperature of 91° C. The operatingconditions in the distillation column B (crude purification step) wereas follows: a pressure of 0.75 MPa, a column top temperature of 65° C.,and a column bottom temperature of 92° C. The column top fractionobtained from the distillation column B (crude purification step), whichcontains HF and 2-chloro-3,3,3-trifluoropropene as main components, wassupplied to the reactor 2 in the next tetrafluoropropene-producingprocedure, and the column bottom fraction, which contains HF as a maincomponent, was recycled to the reactor 1.

A Hastelloy reactor with a capacity of 7.8 L was used as a reactor forthe tetrafluoropropene-producing procedure (reactor 2), and 6.5 kg ofchromium oxide containing CrO₂ as a main component was placed in thereactor as a catalyst. The operating conditions in the distillationcolumn C were as follows: a pressure of 0.75 MPa, a column toptemperature of 3.7° C., and a column bottom temperature of 92° C.

Fluorination treatment of the catalyst before the reaction in thereactor 1 (trifluoropropene-producing step) and the catalyst before thereaction in the reactor 2 (tetrafluoropropene-producing procedure) andheating of the reactors were performed in the same manner as inExample 1. Thereafter, an operation of the process started under theoperating conditions shown in Table 11. The composition of components ineach step of the reaction process was analyzed using gas chromatographyin the same manner as in Example 1. Table 12 shows the results.

TABLE 11 Reaction Temperature Pressure Reaction Step (° C.) (MPa)Reactor 1 300 0.1 Reactor 2 365 0.1 Column Top Column Bottom TemperatureTemperature Pressure Distillation Step (° C.) (° C.) (MPa) Distillation−31 91 0.75 Column A Distillation 65 92 0.75 Column B Distillation 3.792 0.75 Column C

TABLE 12 O₂ HCl HF 1234yf 245cb 1233xf 240db (kmol/hr) (kmol/hr)(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) {circle around (1)}0.00 0.00 5.10 0.00 0.00 0.00 1.50 {circle around (2)} 0.00 0.00 30.00.00 0.00 0.01 1.50 {circle around (3)} 0.00 6.00 25.5 0.00 0.00 1.510.00 {circle around (4)} 0.00 5.94 0.00 0.00 0.00 0.00 0.00 {circlearound (5)} 0.00 0.06 25.5 0.00 0.00 1.51 0.00 {circle around (6)} 0.000.06 0.60 0.00 0.00 1.49 0.00 {circle around (7)} 0.00 0.00 24.9 0.000.00 0.01 0.00 {circle around (8)} 1.02 0.00 1.00 0.00 0.00 0.00 0.00{circle around (9)} 1.02 0.06 93.6 0.01 0.30 9.34 0.00 {circle around(10)}  1.02 1.54 92.0 1.50 0.30 7.85 0.00 {circle around (11)}  1.021.54 0.00 1.49 0.00 0.00 0.00 {circle around (12)}  0.00 0.00 92.0 0.010.30 7.85 0.00

As is clear from Tables 11 and 12, 2,3,3,3-tetrafluoropropene can becontinuously obtained in the process shown in FIG. 1; however, since adistillation column for separating HCl is disposed for each of thetrifluoropropene-producing step and the tetrafluoropropene-producingprocedure, cooling must be performed for each distillation step. It isthus necessary to repeat heating and cooling during each reaction stepand each distillation step respectively, and it is clear that thisprocess increases energy costs and equipment costs.

1. A method for producing 2,3,3,3-tetrafluoropropene, comprising thereaction steps of: (1) obtaining 2-chloro-3,3,3-trifluoropropene byreacting a fluorinating agent with at least one chlorine-containingcompound selected from the group consisting of1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and1,1,2,3-tetrachloropropene; and (2) obtaining 2,3,3,3-tetrafluoropropeneby reacting the 2-chloro-3,3,3-trifluoropropene with anhydrous hydrogenfluoride in a gas phase in the presence of a fluorination catalyst whileheating, the method further comprising the step of supplying theproducts of reaction step (1) and the products of reaction step (2) tothe same distillation apparatus to separate the products into a hydrogenchloride-containing fraction and a fraction substantially free ofhydrogen chloride.
 2. A method for producing 2,3,3,3-tetrafluoropropene,comprising the reaction steps of: (1) obtaining2-chloro-3,3,3-trifluoropropene by reacting a fluorinating agent with atleast one chlorine-containing compound selected from the groupconsisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene; (2)obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to the 2-chloro-3,3,3-trifluoropropene; and (3) obtaining2,3,3,3-tetrafluoropropene by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane, the method further comprising thestep of supplying the products of two or more of reaction steps (1) to(3) to the same distillation apparatus to separate the products into ahydrogen chloride-containing fraction and a fraction substantially freeof hydrogen chloride.
 3. The method for producing2,3,3,3-tetrafluoropropene according to claim 1, wherein reaction step(1) is performed by reacting anhydrous hydrogen fluoride with at leastone chlorine-containing compound selected from the group consisting of1,1,1,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, and1,1,2,3-tetrachloropropene in a gas phase in the presence of afluorination catalyst while heating.
 4. A method for producing2,3,3,3-tetrafluoropropene, comprising the reaction steps of: (1)obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to 2-chloro-3,3,3-trifluoropropene; and (2) obtaining2,3,3,3-tetrafluoropropene by dehydrochlorination of the2-chloro-1,1,1,2-tetrafluoropropane, the method further comprising thestep of supplying the products of reaction step (1) and the products ofreaction step (2) to the same distillation apparatus to separate theproducts into a hydrogen chloride-containing fraction and a fractionsubstantially free of hydrogen chloride.
 5. The method for producing2,3,3,3-tetrafluoropropene according to claim 1, further comprising thestep of removing hydrogen chloride from the hydrogen chloride-containingfraction.
 6. The method for producing 2,3,3,3-tetrafluoropropeneaccording to claim 5, further comprising the step of recycling all orpart of the fraction from which hydrogen chloride has been removed to atleast one of the reaction steps.
 7. The method for producing2,3,3,3-tetrafluoropropene according to claim 1, further comprising thestep of collecting 2,3,3,3-tetrafluoropropene from the hydrogenchloride-containing fraction and/or the fraction substantially free ofhydrogen chloride.
 8. The method for producing2,3,3,3-tetrafluoropropene according to claim 1, further comprising thestep of recycling all or part of the fraction substantially free ofhydrogen chloride to at least one of the reaction steps.
 9. A method forproducing 2-chloro-1,1,1,2-tetrafluoropropane, comprising the reactionsteps of: (1) obtaining 2-chloro-3,3,3-trifluoropropene by reacting afluorinating agent with at least one chlorine-containing compoundselected from the group consisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene; and(2) obtaining 2-chloro-1,1,1,2-tetrafluoropropane by adding hydrogenfluoride to the 2-chloro-3,3,3-trifluoropropene, the method furthercomprising the step of supplying the products of reaction step (1) andthe products of reaction step (2) to the same distillation apparatus toseparate the products into a hydrogen chloride-containing fraction and afraction substantially free of hydrogen chloride.
 10. The method forproducing 2-chloro-1,1,1,2-tetrafluoropropane according to claim 9,wherein reaction step (1) is performed by reacting anhydrous hydrogenfluoride with at least one chlorine-containing compound selected fromthe group consisting of 1,1,1,2,3-pentachloropropane,2,3-dichloro-1,1,1-trifluoropropane, and 1,1,2,3-tetrachloropropene in agas phase in the presence of a fluorination catalyst while heating. 11.The method for producing 2-chloro-1,1,1,2-tetrafluoropropane accordingto claim 9, further comprising the step of removing hydrogen chloridefrom the hydrogen chloride-containing fraction.
 12. The method forproducing 2-chloro-1,1,1,2-tetrafluoropropane according to claim 11,further comprising the step of recycling all or part of the fractionfrom which hydrogen chloride has been removed to at least one of thereaction steps.
 13. The method for producing2-chloro-1,1,1,2-tetrafluoropropane according to claim 9, furthercomprising the step of collecting 2-chloro-1,1,1,2-tetrafluoropropanefrom the hydrogen chloride-containing fraction and/or the fractionsubstantially free of hydrogen chloride.
 14. The method for producing2-chloro-1,1,1,2-tetrafluoropropane according to claim 9, furthercomprising the step of recycling all or part of the fractionsubstantially free of hydrogen chloride to at least one of the reactionsteps.